Fungicidal guanidines

ABSTRACT

Guanidines I ##STR1## (A=C 5  -C 12  -cycloalkyl which may bear up to three further substituents; benzyl substituted in the para-position; R 1 , R 2 , R 3  =H, C 1  -C 4  -alkyl; R 4  -C 5  -C 18  -alkyl which may be interrupted by oxygen, C 5  -C 18  -alkenyl, C 4  -C 18  -alkynyl or phenyl-C 1  -C 6  -alkyl, and these groups may bear up to three further substituents and the phenyl moiety of the phenylalkyl may additionally bear a phenoxy group or up to three C 2  -C 4  -alkenyl, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl, C 1  -C 6  -alkyl or haloalkyl groups, C 5  -C 6  -cycloalkyl-C 1  -C 8  -alkyl, where the ring may bear up to three further substituents; A=benzyl and R 4  =C 3  -C 4  -alkyl which may be interrupted by oxygen, or C 4  -alkenyl, both of which may bear up to three further substituents; R 3  +R 4  =C 5  -C 6  -heterocycle which may bear up to three further substituents and may be interrupted by oxygen) and the salts I.HX and the metal complexes of I. 
     The compounds I are suitable as fungicides.

The present invention relates to novel guanidines of the formula I ##STR2## where A is cycloalkyl which has 5 to 12 carbon atoms in the ring and may carry up to three of the following substituents: hydroxyl, halogen, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -haloalkyl and C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl; or benzyl which is substituted in the para position by C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkoxy, where the substituent may furthermore carry a hydroxyl or a C₁ -C₆ -alkoxy group;

R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl, and

R⁴ is C₅ -C₁₈ -alkyl which may be interrupted by oxygen, or is a C₅ -C₁₈ -alkenyl group, a C₁ -C₁₈ -alkynyl group or a phenyl-C₁ -C₆ -alkyl group, where these groups may carry up to three of the following substituents: hydroxyl, halogen, cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino or di-(C₁ -C₄)-alkylamino substituents and the phenyl moiety of the phenylalkyl group may additionally carry a phenoxy group or up to three C₂ -C₄ -alkenyl groups, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl groups or C₁ -C₆ -alkyl groups which may be unsubstituted or partially or completely halogenated, or C₅ -or C₆ -cycloalkyl-C₁ -C₈ -alkyl where the cycloalkyl ring may carry up to three C₁ -C 4-alkyl groups or up to two hydroxyl or trifluoromethyl groups; or, where A is a benzyl group according to the definition, C₃ -or C₄ -alkyl which may be interrupted by oxygen or may carry a C₄ -alkenyl group, where these groups may carry up to three of the following substituents: hydroxyl, halogen, cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino or C₂ -C₈ -dialkylamino groups; or, together with the radical R³ and the nitrogen atom, may form a 5-membered or 6-membered heterocyclic ring which may be monosubstituted to trisubstituted by C₁ -C₆ -alkyl, phenyl or C₁ -C₆ -alkylphenyl or may be interrupted by an oxygen atom,

and the plant-tolerated mineral acid salts I·HX and metal complexes of I.

The present invention frthermore relates to processes for the preparation of these compounds, their use as fungicides, and fungicides which contain these compounds as active substances.

The monograph Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel, Volume 4, Springer Verlag 1977, page 145 et seq., discloses fungicidal alkylguanidine salts (dodines) and bisalkylguanidineamine salts (guazatines) which carry an alkyl group on one of the guanidine nitrogen atoms or whose guanidino groups are linked to one another by an azaalkylene group.

Guanidine derivatives which have a fungicidal action and are aryl-substituted at one nitrogen atom and substituted by alkyl and cycloalkyl groups at the two other nitrogen atoms are described in DE-Al-31 08 564.

However, the actions of these compounds may be satisfactory only under certain circumstances, particularly in the case of low application rates and concentrations. In particular, some of them cause damage to crops.

It is an object of the present invention to provide novel fungicidal compounds which, even at relatively low application rates, have better fungicidal properties than the compounds known to date, without causing significant damage to the crops.

We have found that this object is achieved by the guanidines of the formula I which were defined at the outset. We have also found processes for the preparation of these guanidines.

If R¹ and/or R³ are hydrogen, the compounds I may furthermore be present in tautomeric forms, which are described by formula I.

The substituents in the novel compounds I have the following specific meanings:

A is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl, where these groups may carry up to three of the following radicals:

hydroxyl;

halogen, including in particular fluorine;

straight-chain or branched C₁ -C₁₀ -alkyl, in particular C₁ -C₆ -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl or 2,4,4-trimethylpent-2-yl; straight-chain or branched C₁ -C₁₀ -alkoxy, in particular C₁ -C₆ -alkoxy, such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy or octyloxy; straight-chain or branched, partially or completely halogenated C₁ -C₁₀ -haloalkyl, in particular haloalkyl, such as trifluoromethyl or pentafluoroethyl;

C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl, in particular C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, such as methoxymethyl, ethoxymethyl, methoxyethyl, tert-butoxymethyl or 1-methoxy-1methylethyl; or

benzyl which may carry one of the following substituents in the para position:

straight-chain or branched C₁ -C₁₀ -alkyl, in particular C₁ -C₆ -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylethyl, 1,1-dimethylpropy1,2,3-dimethylpropyl, 1,1,2-trimethylpropyl, 2-hydroxyprop-2-yl or 2-methoxyprop-2-yl;

C₁ -C₁₀ -alkoxy, in particular C₁ -C₆ -alkoxy, such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy

or hexyloxy;

particularly preferred radicals A are cyclopentyl, cyclohexyl, cycloheptyl, 1-methoxy-1-methylethylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 3-trifluoromethylcyclohexy, 1,3,3-dimethylcyclohexy1,3,3,5-trimethylcyclohexyl, 4-hydroxycyclohexyl, 4-chlorocyclohexyl, 4-chloroethylcyclohexyl, 4-isopropylcyclohexyl, 4-(1-methoxyisopropyl-cyclohexyl, 4-tert-butylcyclohexyl, 4-(1,1-dimethylpropyl)-cyclohexyl, 4-ethoxycyclohexyl, 4-tertbutoxycyclohexyl, 4-(2,4,4-trimethylhex-2-yl)-cyclohexyl, benzyl, p-methylbenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-(2,3-dimethylpropyl)-benzyl, p-(1,1-dimethylethyl)-benzyl, p-(1,1,2-trimethylpropyl)benzyl, p-(2-hydroxyprop-2-yl)-benzyl, p-(2-methoxyprop- 2-yl)-benzyl, p-methoxybenzyl or p-tert-butoxybenzyl; R¹, R² and R³ are each preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl or isobutyl; R⁴ is straight-chain or branched C₅ -C₁₈ -alkyl which may be interrupted by oxygen, preferably 2,2-dimethylpropyl, 3methylbutyl, 3,3-dimethylbutyl, n-pentyl, 4,4-dimethylpentyl, n-hexyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, n-heptyl, n-octyl, 5-methyloct-2-yl, 2-hydroxyoctyl, 8-hydroxyoctyl, 8-fluorooctyl, 8-chlorooctyl, 2,5,7,7-tetramethyloctyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, isotridecyl, 6,10-dimethylundec-2-yl, 6,10,14-trimethylpentadec2-yl, n-hexadecyl, n-octadecyl, 4-(4-tert-butoxy)-but-2 -yl, tert-butoxypentyl, 6-ethyl-4-oxadecyl or 3-diethylaminopropyl;

straight-chain or branched C₅ -C₁₈ -alkenyl or C₄ -C₁₈ -alkyn-yl, in particular dimethylallyl or but-2-ynyl; phenyl-C₁ -C₆ -alkyl, in particular phenyl-C₁ -C₄ -alkyl, which may carry a phenoxy group or up to three of the following radicals:

hydroxyl;

halogen, including in particular fluorine or

chlorine;

cyano;

straight-chain or branched C₁ -C₇ -alkoxy, in particular C₁ -C₄ -alkoxy, such as methoxy, ethoxy, isopropoxy, n-butoxy or tert-butoxy, or up to 2 amino, C₁ -C₄ -alkylamino and/or di-C₁ -C₄ -alkylamino substituents, in particular amino, dimethylamino and diethylamino;

phenoxy on the phenyl moiety of the phenylalkyl group;

up to three of the following substituents on the phenyl moiety of the phenylalkyl group:

straight-chain or branched C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, in particular C₁ -C₄ -alkoxy-C₁ -or -C₂ -alkyl, such as methoxymethyl, ethoxymethyl or ethoxyethyl;

straight-chain or branched C₂ -C₄ -alkenyl, in particular ethenyl or isopropenyl;

C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, such as methoxymethyl, or

straight-chain or branched C₁ -C₆ -alkyl or partially or completely halogenated C₁ -C₆ -haloalkyl, in particular methyl, trichloromethyl, trifluoromethyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, 1,1-dimethylpropyl, 1,1,2-trimethylpropyl, 2,4,4-trimethylpentyl- or perfluoropentyl;

particularly preferred radicals are benzyl, 4-hydroxybenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 4-cyanobenzyl, 4-methylbenzyl, 4-trifluoromethylbenzyl, 4-trichloromethylbenzyl, 4-isopropylbenzyl, 4-isopropenylbenzyl, 3-tert-butylbenzyl, 4-tert-butylbenzyl, 4-(1,1-dimethylpropyl)-benzyl, 4-(1,1,2-trimethylpropyl)-benzyl, 4-(2,4,4-trimethylpentyl)-benzyl, 4-(1-hydroxy-1-methylethyl)-benzyl, 3,5-di-tert-butyl-4-hydroxybenzyl, 4-methoxybenzyl, 4-(1-methoxy-1-methylethyl)-benzyl, 4-n-butoxybenz-yl or 4-tert-butoxybenzyl, 1-phenylethyl, phenethyl, 4-methoxyphenethyl, 4-tert-butylphenethyl, 3-phenylpropyl, 3-(4-tert-butylphenyl)-2-methylpropyl or 4-phenylbut-2-yl;

a C₅ - or Cs-cycloalkyl-C₁ -C₈ -alkyl group where the cycloalkyl ring may carry up to three C₁ -C₄ -alkyl groups, such as methyl or tert-butyl, or up to two hydroxyl or trifluoromethyl groups, in particular a C₅ - or C₆ -cycloalkyl-C₁ -C₄ -alkyl group, such as cyclohexylmethyl, 4-tert-butylcyclohexylmethyl, 4-trifluoromethylcyclohexylmethyl, 4-hydroxycyclohexylmethyl, 4-tert-butoxycyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl or 3-(4-tert-butyl-cyclohexyl)-2-methylpropyl;

or, where A is a benzyl group according to the definition,

straight-chain or branched C₃ - or C₄ -alkyl which may be interrupted by oxygen, in particular isopropyl, tert-butyl or 2-hydroxypropyl; or C₄ -alkylene, in particular but-2-enyl;

or, together with R³ and the nitrogen atom, is a 5-membered or 6-membered heterocyclic structure which may be monosubstituted to trisubstituted by C₁ -C₆ -alkyl, phenyl or C₁ -C₆ -alkylphenyl and may be interrupted by an oxygen atom; in particular 2-(1,5-dimethylhexyl)pyrrolidinyl, 2-(2,4,4-trimethylpentyl)-pyrrolidinyl, 3-phenylpyrrolidinyl, 3-(4-tert-butylphenyl)-pyrrolidinyl, 3-(4-tert-butylphenyl)-4-methylpyrrolidinyl, piperidinyl, 4-tert-butylpiperidinyl, 4-(4-tert-butylphenyl)piperidinyl, morpholinyl or 2,6-dimethylmorpholin-4-yl.

Particularly suitable compounds I are shown in the Table, those which carry the following substituents being particularly preferred:

A is cyclohexyl, 3,3-dimethylcyclohexyl, 4-tert-butylcyclohexyl or p-tert-butylbenzyl;

R¹ is hydrogen;

R² is hydrogen or C₁ -C₄ -alkyl;

R³ is hydrogen or methyl; and

R⁴ is C₆ -C₁₄ -alkyl, in particular 2-ethylhexyl or 6,1-dimethylundec-2-yl-, or

p-(C₁ -C₆ -alkyl)-phenyl-C₁ -C₄ -alkyl, in particular p-tert-butylbenzyl, 3-(p-tert-butylphenyl)-2-methylpropyl or p-(2,3-dimethylbut-2-yl)-benzyl, or

together with R³ and the nitrogen atom, forms 4-tert-butylphenylpyrrolidinyl.

Suitable acid addition salts are the planttolerated salts of acids which do not adversely affect the fungicidal action of I, for example the iodides, chlorides, bromides, hydrochlorides, hydrobromides, sulfates, dodecylsulfates, nitrates, carbonates, phosphates, formates, acetates, propionates, benzoates, oxalates, naphthalenesulfonates,dodecylbenzenesulfonates,lactates and the salts with the anion of saccharin. The iodides, chlorides and acetates are preferred.

Suitable metal complexes are the complexes of copper, of zinc, of tin, of manganese, of iron, of cobalt or of nickel. The complexes are preferably prepared from the free bases I and salts of mineral acids, for example the chlorides or sulfates, with the metals.

The following compounds I are very particularly suitable:

N-1-cyclohexyl-N-2-(6,10-dimethylundec-2-yl)-guanidine hydriodide,

N-1-cyclohexyl-N-2-[3-(p-tert-butylphenyl)-2-methyl-propyl]-guanidine hydriodide,

N-1-(2,2-dimethylcyclohexyl)-N-2-[3-(p-tert-butylphenyl)2-methylpropyl]-guanidine hydriodide,

N-1-cyclohexyl-N-2-(p-tert-butylbenzyl)-guanidine hydrochloride,

N-1-(3,3-dimethylcyclohex-Y1)-N-2-(p-tert-butylbenzyl)guanidine hydrochloride,

N-1-cyclohexyl-N-2-[p-(2,3-dimethylbut-2-yl)-benzyl]guanidine hydriodide,

N-1-(p-tert-butylcyclohexyl)-N-2-(p-tert-butylbenz-yl)-N-3-methylguanidine hydriodide,

N-1-cyclohexyl-N-2-n-butyl-N-3-(p-tert-butylbenzyl)guanidine hydroacetate,

N-1-cyclohexyl-N-2-(p-tert-butylbenzyl)-N-2-methylguanidine hydroacetate,

N-1-(p-tert-butylbenzyl)-N-2-(2-ethylhexyl)-guanidine hydriodide,

N-1-(p-tert-butylbenzyl)-N-2-(p-tert-butylbenzyl)-N3-methylguanidine hydriodide and

1-{[(3,3-dimethylcyclohexyl)-amino]-iminomethyl}-[3-(p-tert-butylphenyl)]-pyrrolidine.

The guanidines I are obtainable in various ways, preferably by the following methods:

(a) Preparation from thiuronium salts and amines ##STR3##

In these formulae, R⁵ is benzyl or a short-chain alkyl radical, eg. methyl or ethyl, and X, is advantageously chloride, bromide, iodide, sulfate, methylsulfate, methylsulfonate or tosylate.

The starting compounds IIa-IIc and IIIa-IIIc are known or are obtainable in a known manner; regarding the thiuronium saits, reference may be made to Houben-Weyl, Methoden der Organischen Chemie, 4th edition, Vol. IX, page 900 et seq.

The reaction, known per se from Houben-Weyl, Methoden der Organischen Chemie, 4th edition, Vol. VIII, page 1893 et seq. and Vol. E4, page 614 et seq., of thiuronium salts with amines to give the guanidine derivatives I·HX' is preferably carried out in polar solvents such as alcohols, ketones, ethers, nitriles, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide or dimethylacetamide.

The ratios of the reactants may be varied depending on the compounds used. Advantageously, equimolar amounts are reacted or, particularly preferably, twice the required amount of the amine component is used. Furthermore, a tertiary amine, such as triethylamine, may also be added as an auxiliary base to trap the mercaptan being formed. In this case, equimolar amounts, based on the thiuronium salt, of the auxiliary base are preferably used.

It is advisable to carry out the reactions at from 20° C. to the boiling point of the solvent, preferably from 60 to 130° C. Since the reactions are not pressuredependent, they are preferably carried out under atmospheric pressure.

By anion exchange, it is possible to obtain salts with other anions X⊖ or, in the case of exchange with hydroxyl ions, the free bases I.

(b) Preparation from aminoiminomethanesulfonic acids and amines ##STR4##

The starting compounds IVa-IVd are known or are obtainable in a known manner from thiourea derivatives (eg. C.A. Maryanoff et al., J. Org. Chem 51 (1986), 1982 et seq.).

The reaction, known per se from C.A. Maryanoff et al., loc. cit., of aminoiminosulfonic acids with amines to give the guanidine derivatives I is preferably carried out in a polar solvent, such as an alcohol or, particularly preferably, in acetonitrile.

It si advisable to carry out the reactions at from 0° C. to the boiling point of the solvent.

Regarding the ratios and the pressure, the data for Method (a) are applicable.

(c) Preparation from carbodiimides and amines ##STR5##

The starting compounds Va-Vc are known or are obtainable by known processes. By way of example, reference may be made to M. Mikolaiczyk, Tetrahedron 37 (1981), 233 et seq., Z.M. Jaszay et al., Synthesis, 1987, et seq., and G. Appel et al., Chem. Ber. 104 (1971), 1335 et seq.

The reaction, known per se from Houben-Weyl, Methoden der Organischen Chemie, 4th edition, Vol. VIII, page 180 and Vol. E4, page 609, of carbodiimides with amines to give the guanidine derivatives I is preferably carried out in a nonpolar solvent, such as hexane, toluene, a short-chain alcohol, such as methanol or isopropanol, or a nitrile, such as acetonitrile.

For the reactions, it is advisable to use equimolar amounts of the starting compounds or, preferably, a small excess of the amine component, ie. not more than about 10%.

Regarding the temperature and the pressure, the data for Method (a) are applicable.

(d) Preparation from diphenylimidocarbonates and amines ##STR6## In formula IVa, R⁶ is cyano, benzoyl or methanesulfonyl.

The reaction, known per se from A. Buschauer, Arzneim.-Forsch./Drug Res. 37 (II) (1987), 1003/1008 et seq., and Arch. Pharm. 321 (1988), 281, of diphenylimidodicarbonates with two amines is carried out in two separate stages. The reaction of the imidocarbonate with the first amine is preferably effected in a chlorohydrocarbon, such as methylene chloride, in ether, such as tetrahydrofuran or diethyl ether, or a nitrile, such as acetonitrile. The further reaction of the product with the second amine is carried out in a polar solvent, such as acetonitrile or pyridine.

Regarding the ratios, the temperature and the pressure, the data for Method (c) are applicable.

The hydrolysis of the resulting bases I where R² =R⁶ is carried out in a known manner, advantageously in a mineral acid at, for example, from 70 to 120° C. Preferably, 2-12.5 M hydrochloric acid is used under reflux.

The chloride salts of the novel compounds I in which R² is hydrogen are obtained.

(e) Preparation from cyanogen bromide and amines ##STR7## In these formulae, X" is preferably chloride.

The reaction, known per se from H.W. Geluk et al., J. Med. Chem. 12 (1969), 712 et seq., of cyanogen bromide with amines to give N-substituted cyanamide derivatives VIIa or VIIb is preferably carried out in an ether, such as diethyl ether or tetrahydrofuran.

An excess of the amine component over the cyanogen bromide, ie. not more than about 60%, is advantageously used.

It is advisable to carry out the reaction at from 0 to 25° C. Since the reactions are not pressuredependent, they are preferably effected under atmospheric pressure.

The reaction of the N-substituted cyanamides VIIa and VIIb with the hydrochlorides of the amines IIIb and IIIa is preferably carried out in the absence of a solvent, at, for example, from 150 to 250° C.

Regarding the amounts used, the pressure or the preparation of the free bases I, the data for Method c) are applicable.

The compounds of the formula I and their salts and metal complexes according to the definition are suitable as fungicides and are well tolerated by plants.

Generally speaking, the guanidines according to the invention are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cerospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fursarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The guanidines I are particularly suitable for combating Botrytis cinerea.

The compounds are applied by treating the plants, or the seed, materials or soil to be protected against fungus attack with a fungicidally effective amount of the active ingredients.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), praffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and emthylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The application rates are from 0.01 to 6, and especially from 0.02 to 3, kg of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials (wood), for example against Paecilomyces variotii.

When the active ingredients are sued for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are usually employed.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. A solution of 90 parts by weight of compound no. 3a and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 2a 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil; by finely distributing the solution in water a dispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 5a, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound no. 26a, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

V. A mixture, triturated in a hammer mill, of 80 parts by weight of compound no. 37a, 3 parts by weight of the sodium salt of diisobutylnapthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel; by finely distributing the mixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound no. 1b and 97 parts by weight of particulate kaolin. This dust contains 3% by weight of the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 2b, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel; this formulation of the active ingredient has good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 4b, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water; this dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 9b, 2 parts by weight of the calcium slat of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a pheolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.

In these applications forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.

MANUFACTURING EXAMPLES Example A, according to method (a) (compound 7b in table) N-1-(4-tert.-butylbenzyl)-N-2-methyl-N-3-(3,5,5-trimethyl-hexyl)-guanidine hydroiodide ##STR8##

Under a nitrogen blanket, a mixture of 19 g (0.05 mol) of N-(4-tert.-butylbenzyl)-N'-, S-dimethylisothiuronium iodide, 14.1 g (0.1 mol) of 3,5,5-trimethylhexylamine, 5 g (0.05 mol) of triethylamine and 20 g of molecular sieve (4A) in 200 ml of anhydrous acetonitrile was refluxed for 6 hours with elimination of methanethio. After filtration while hot, the mixture was worked up in the usual manner.

Yield: 64% of theory; m.p. 165° C.

Intermediate state Al N-(4-tert.-Butylbenzyl)-N'-methylthiourea ##STR9##

At 20 to 30° c., a solution of 163 g (1 mol) of 4-tert.-butylbenzylamine in 100 ml of anhydrous acetonitrile was dripped, while cooling, into a mixture of 73 g (1 mol) of methyl isothiocyanate in 80 ml of anhydrous acetonitrile. The mixture was stirred for 3 hours at 20° C. and then for a further hour at 80 to 90° C. before being evaporated down. The crude product was precipitated with hexane from ethyl acetate, washed with hexane and dried under reduced pressure at 60° c.

Yield: 72% of theory; mp 72° C.

Intermediate state A2 N-(4-tert-Butylbenzyl)-N'-S-dimethylisothiuronium iodide ##STR10##

A solution of 23.6 g (0.1 mol) of N-(4-tert.-butylbenzyl)-N'-methylthiourea and 114.2 g (0.1 mol) of iodomethane in 200 ml of methanol was reluxed for one hour. After the mixture had cooled to room temperature the product was precipitated by adding methyl tert-butyl ether, washed and dried under reduced pressure at 40° C.

Yield: 53% of theory; mp: 172° C.

Example B, according to method (a) (compound 20b in table) N-1-(4-tert.-Butylbenzyl)-N-2-n-octylguanidin hydroiodide ##STR11##

A mixture of 9.1 g (2,5·10⁻² mol) of N-(4-tert.-butylbenzyl)-S-methylisothiuronium iodide, 6.5 g (5·10⁻² mol) of n-octylamine, 2.5 g (25 mmol) of trithylamine, 3 g of molecular sieve (4 A) and 200 ml of acetonitrile was refluxed for 48 hours and worked up as described in Example A.

Yield: 61% of theory; mp.: 113° C.

Intermediate stage B1 N-(4-tert.-Butylbenzyl)-thioure ##STR12##

Over a period of 10 minutes, a solution of 147.5 g (1.05 mol) of benzoyl chloride was dripped into a solution of 82.5 g (1.1 mol) of ammonium thiocyanate in 300 ml of absolute acetone. After the mixture had been stirred for 10 minutes at the reflux temperature, a solution of 163 g (1 mol) of 4-tert.-butylbenzylamine in 150 ml of acetone was dripped in, and the reaction mixture was reluxed for 20 minutes and stirred into 2 liters of ice water. The precipitated solid was washed with water, dissolved in a hot mixture of 1 liter of 10% strength caustic solution and 550 ml of ethanol and refluxed for a further 15 minutes.

The mixture was then diluted with ice water, adjusted with concentrated hydrochloric acid to a pH of 1 and then with solid sodium bicarbonate to a pH of about 9. The resulting precipitate was washed with water and dried under reduced pressure at 60° C.

Yield: 92% of theory; mp.:80° C.

Intermediate state B2 N-(4-tert.-Butylbenzyl)-S-methylisothiuronium iodide ##STR13##

At 30 to 40° C., 54.5 g (0.333 mol) of iodomethane was dripped into 85 g (0.383 mol) of N-(4-tert.-butylbezyl)-thiourea in 200 ml of methanol. The mixture was reacted and worked up analogously to Example A, intermediate state A2; the product was dired at 60° C.

Yield: 74% of theory; mp.: 143° C.

Example C, according to method (a) (example 1a in table) N-1-Cyclohexyl-N-2-(4-tert.-butylbenzyl)-guanidine hydroiodide ##STR14##

30 g (0.1 mol) of N-cyclohexyl-S-methylisothiuronium iodide, 32.6 g (0.2 mol) of 4-tert.-butylbenzylamine, 10.1 g (0.1 mol) of triethylamine and 3 g of molecular sieve (4 A) were reacted for 48 hours in 200 ml of anhydrous acetonitrile analogously to Example A.

Yield: 95% of theory; mp.: 145-150° C.

Example D, according to method (a) (example 41a in table) N-1-(3-methyl-cyclohexyl)-N-2-(4-tert.-butylbezyl)-N-3-methylguanidine hydroiodide ##STR15##

9.5 g (25 mmol) of N-(4-tert.-butylbenzyl)-N',S-dimethylisothiuronium iodide, 5.7 g (50 mmol) of 3-methylcyclohexylamine (isomer mixture), 2.5 g (25 mmol) of triethylamine and 1.5 g of molecular sieve (4 A) in 100 ml of acetonitrile were reacted for 2 hours analogously to Example A.

Yield: 25% of theory; mp.: 150° C.

Example E, according to method (c) (example 11 b in table) N-1-(4-tert.-Butylbenzyl)-N-2-n-butyl-N-3-(2,2-dimethylpropyl)-guanidine hydrochloride ##STR16##

A mixture of 2 g (8,2·10⁻³ mol) of N-(4-tert.-butylbenzyl)-N'-n-butyl-carbodiimide, 0.17 g (8,2·10⁻³ mol) of 2,2-dimethylpropylamine and 100 ml of anhydrous tert.-butanol was refluxed for 24 hours. An oily product was isolated, methanolic hydrochloric acid was added, and the mixture was concentrated under reduced pressure and crystallized by trituration with methyl tert.-butyl ether.

Yield: 33% of theory; mp.: 88° C.

Example F, according to method (c) (example 57a in table) N-1-(4-tert.-butyl-cyclohexyl)-N-2-n-butyl-N-3-(4-tert.-butylbenyl)-guanidin hydrochloride ##STR17##

2 g (8,2·10⁻³ mol) of N-(4-tert.-butylbenzyl)-N'-n-butylcarbodiimide and 1.27 g (8,2·10³ mol) of 4-tert.-butylcyclohexylamine were reacted analogously to Example E.

Yield: 30% of theory; mp.: 110° C.

Example G (example 30a in table) N-1-cyclohexyl-N-2-[3-(4-tert.-butylphenyl)-2-methylpropyl]-guanidine hydrochloride ##STR18##

21.8 g (6,6·10⁻² mol) of N-1-cyclohexyl-N-2-[3-(4-tert.-butylphenyl)-2-methylpropyl]guanidine hydroiodide (example 26a from Table 1) in 300 of methanol/water (1:1) were filtered through a column containing 250 g of Amberlyst A 26 (OH⊖ form). After working up, the free guanidine obtained was converted into the hydrochloride with an excess of methanolic hydrochloric acid.

Yield: 80%; mp.: 169° C.

The compounds listed in Table 1 below were obtained analogously to Examples A to G;

                                      TABLE 1                                      __________________________________________________________________________      ##STR19##                                                                     Comp.                                                                          No.  A        R.sup.1                                                                            R.sup.2                                                                             R.sup.3                                                                               R.sup.4      HX      mp./IR                                                                         (film)[cm.sup.-1            __________________________________________________________________________                                                        ]                           1a   cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         HI      145° C.              2a   cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      180° C.              3a   cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         HI      140° C.              4a   cyclohexyl                                                                              CH.sub.3                                                                           H    H      4-tert.-butylbenzyl                                                                         HI      152° C.              5a   cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         HCl     195° C.              6a   cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          195° C.              7a   cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                           1719, 1703, 1615,                                                              1515,                                                                          1445, 1403, 1230,                                                              1202,                                                                          1173, 721                   8a   cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          2930, 2854, 1586,                                                              1514,                                                                          1463, 1450, 1393,                                                              1364                        9a   cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HCl     3253, 3200, 3102,                                                              2932,                                                                          2856, 1625, 1451,                                                              1366,                                                                          1347, 1174                  10a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         --      2936, 1652, 1606,                                                              1487,                                                                          1398, 1094, 1072,                                                              1007                        11a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         HCl     140° C.              12a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          2962, 2862, 2856,                                                              1667,                                                                          1613, 1567, 1514,                                                              1397                        13a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                           140° C.              14a  cyclohexyl                                                                              H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         --      2957, 2929, 2854,                                                              1634,                                                                          1512, 1449                  15a  cyclohexyl                                                                              H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         HCl     105° C.              16a  cyclohexyl                                                                              H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          resin                       17a  cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         --      3277, 3179, 2960,                                                              2931,                                                                          2854, 1647, 1626            18a  cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         HI      128° C.              19a  cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                       20a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         --                                  21a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         HI                                  22a  cyclohexyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                       23a  cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         --                                  24a  cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI                                  25a  cyclohexyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                       26a  cyclohexyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    HI      80° C.                                             2-methylpropyl                                   27a  cyclohexyl                                                                              H   H    H      4-(2,3-dimethylbut-                                                                         HI      >200° C.                                           2-yl)-benzyl                                     28a  cyclohexyl                                                                              H   H    H      n-tridecyl   HI      3283, 3252, 3181,                                                              2926, 2854,                                                                    1646, 1631, 1466,                                                              1452, 1369                  29a  cyclohexyl                                                                              H   H    H      6,10-dimethylundec-2-yl                                                                     HI      3268, 3185, 2928,                                                              2855,                                                                          1667, 1646, 1624,                                                              1451                        30a  cyclohexyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    HCl     169° C.                                            2-methylpropyl                                   31a  cyclohexyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    1/2(COOH).sub.2                                                                        110° C.                                            2-methylpropyl                                   32a  cyclohexyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          3020, 2959, 2931,                                                              2857,                                                     2-methylpropyl       1648, 1558, 1403,                                                              1363                        33a  cyclohexyl                                                                              H   n-butyl                                                                             H      benzyl       CH.sub.3 COOH                                                                          2932, 2856, 1625,                                                              1596, 1569, 1496,                                                              1452,                                                                          1399, 1377, 1253            34a  cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         --      145° C.              35a  cyclopentyl                                                                             H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         --                                  36a  cyclopentyl                                                                             H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      145° C.              37a  cyclooctyl                                                                              H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI       82° C.              38a  cyclooctyl                                                                              H   H    CH.sub.3                                                                              4-tert.-butylbenzyl                                                                         --                                  39a  cyclododecyl                                                                            H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      124° C.              40a  cyclododecyl                                                                            H   H    H      4-tert.-butylbenzyl                                                                         HI      170° C.              41a  3-methyl-                                                                               H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      150° C.                   cyclohexyl                                                                42a  4-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      220° C.                   cyclohexyl                                                                43a  4-tert.-butyl-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         HI      200° C.                   cyclohexyl                                                                44a  4-tert.-butyl-                                                                          H   H    H      4-tert.-butyloxybenzyl                                                                      HI      206° C.                   cyclohexyl                                                                45a  4-isopropyl-                                                                            H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      2959, 2933, 2867,                cyclohexyl                                    1634, 1513, 1366            46a  4-isopropyl-                                                                            H   H    H      4-tert.-butyloxybenzyl                                                                      HI                                       cyclohexyl                                                                47a  3,3-dimethyl-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         HI      180° C.                   cyclohexyl                                                                48a  3,3-dimethyl-                                                                           H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       cyclohexyl                                                                49a  3,3-dimethyl-                                                                           H   H    H      3-(4-tert-butylphenyl)-                                                                     HI      110° C.                   cyclohexyl               2-methyl-propyl                                  50a  3-trifluoro-                                                                            H   H    H      4-tert.-butylbenzyl                                                                         HI       90° C.                   methylcyclohexyl                                                          51a  3-trifluoro-                                                                            H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       methylcyclohexyl                                                          52a  3-trifluoro-                                                                            H   H    H      3-(4-tert-butylphenyl)-                                                                     HI       95° C.                   methylcyclohexyl         2-methyl-propyl                                  53a  3,3-dimethyl-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         HCl     >200° C.                  cyclohexyl                                                                54a  3,3-dimethyl-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          120° C.                   cyclohexyl                                                                55a  3,3-dimethyl-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                           155° C.                   cyclohexyl                                                                56a  4-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          2959, 2866, 1629,                                                              1572,                            cyclohexyl                                    1515, 1393, 1366            57a  4-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         HCl     110° C.                   cyclohexyl                                                                58a  3-methyl-                                                                               H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         HCl      75° C.                   cyclohexyl                                                                59a  3-methyl-                                                                               H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          2957, 2929, 2869,                                                              1628,                            cyclohexyl                                    1571, 1515, 1458,                                                              1394,                                                                          1367, 1268                  60a  3-methyl-                                                                               H   H    H      4-tert.-butylbenzyl                                                                         HI      100° C.                   cyclohexyl                                                                61a  2-methyl-                                                                               H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI      102° C.                   cyclohexyl                                                                62a  cyclohexyl                                                                              H   isopropyl                                                                           H      4-tert.-butylbenzyl                                                                         HCl     135° C.              63a  cyclohexyl                                                                              H   but-2-yl                                                                            H      4-tert.-butylbenzyl                                                                         HCl     105° C.              64a  cyclohexyl                                                                              H   H    H      4-chlorobenzyl                                                                              HI       80° C.              65a  cyclohexyl                                                                              H   H    H      2,4-dichlorobenzyl                                                                          HI      3270, 3274, 2931,                                                              1648,                                                                          1624, 1589, 1563,                                                              1544                        66a  cyclohexyl                                                                              H   H    H      4-cyanobenzyl                                                                               --                                  67a  cyclohexyl                                                                              H   H    H      4-trifluoromethylbenzyl                                                                     --                                  68a  cyclohexyl                                                                              H   H    H      1-phenyl-ethyl                                                                              --                                  69a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 3-(4-tert.-butyl-                                                              HI      195° C.                                     phenyl)-pyrroidinyl                                     70a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                               HI      135° C.                                     2-yl)-pyrrolidinyl                                      71a  3,3-dimethyl-                                                                           H   H    R.sup.3 + R.sup.4 = 3-(4-tert.butyl-                                                               HI      170° C.                   cyclohexyl        phenyl)-pyrrolidinyl                                    72a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 4-isopropyl-                                                                   HI      169° C.                                     piperidinyl                                             73a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                               HI      110° C.                                     2-yl)-pyrrolidinyl                                      74a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                               CH.sub. 3 COOH                                                                         3272, 3165, 2931,                                                              2859,                                              2-yl)-pyrrolidinyl          1660, 1617, 1557,                                                              1468,                                                                          1452, 1383                  75a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                               (COOH).sub.2                                                                           3200, 2932, 2859,                                                              1738,                                              2-yl)-pyrrolidinyl          1647, 1620, 1553,                                                              1467,                                                                          1452, 1205                  76a  cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 = (2,4,4-trimethyl-                                                              HI      175° C.                                     pentyl)-pyrrolidinyl                                    77a  4-tert.-butyl-                                                                          H   H    H      3-(4-tert.-butylpenyl)-                                                                     --                                       cyclohexyl               2-methylpropyl                                   78a  4-(2,4,4-tri-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         HI      100° C.                   methylhex-2-yl)-                                                               cyclohexyl                                                                79a  4-(2,4,4-tri-                                                                           H   H    H      3-(4-tert-butylphenyl)-                                                                     --                                       methylhex-2-yl)-         2-methylpropyl                                        cyclohexyl                                                                80a  4-ethoxy-                                                                               H   H    H      4-tert.butylbenzyl                                                                          --                                       cyclohexyl                                                                81a  4-hydroxyethyl-                                                                         H   H    H      4-tert.-butylbenzyl                                                                         --                                       cyclohexyl                                                                82a  4-chlorocyclo-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         --                                       hexyl                                                                     83a  4-tert.-buto-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         --                                       oxycyclohexyl                                                             84a  4-tert.-buto-                                                                           H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       oxycyclohexyl                                                             85a  3,3,5-tri-                                                                              H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       methylcyclohexyl                                                          86a  3,3,5-tri-                                                                              H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       methylcyclohexyl                                                          87a  4-chloroethyl-                                                                          H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       cyclohexyl                                                                88a  4-chloroethyl-                                                                          H   H    H      4-tert.-butyloxybenzyl                                                                      --                                       cyclohexyl                                                                89a  cyclohexyl                                                                              H   H    H      4-hydroxybenzyl                                                                             --                                  90a  cyclohexyl                                                                              H   H    H      4-trichoromethylbenzyl                                                                      --                                  91a  cyclohexyl                                                                              H   H    H      4-methoxybenzyl                                                                             HI       48° C.              92a  cyclohexyl                                                                              H   H    H      2-(4-methoxyphenyl)ethyl                                                                    HI      3249, 3179, 2932,                                                              1647,                                                                          1629, 1513, 1247            93a  cyclohexyl                                                                              H   H    H      C.sub.13 H.sub.27 (isomer                                                                   --xture)                            94a  cyclohexyl                                                                              H   H    H      cyclohexylmethyl                                                                            --                                  95a  cyclohexyl                                                                              H   H    H      2,2-dimethylpropyl                                                                          --                                  96a  cyclohexyl                                                                              H   H    H      n-hexyl      --                                  97a  cyclohexyl                                                                              H   H    H      n-octyl      HI      3285, 3250, 3181,                                                              2929,                                                                          2855, 1647, 1631,                                                              1602                        98a  cyclohexyl                                                                              H   H    H      3-methyl-butyl                                                                              --                                  99a  cyclohexyl                                                                              H   H    H      phenethyl    --                                  100a cyclohexyl                                                                              H   H    H      2-ethylhexyl HI      3284, 3252, 3181,                                                              2958,                                                                          2930, 2857, 1647,                                                              1630                        101a cyclohexyl                                                                              H   H    H      6-ethyl-4-oxadecyl                                                                          --                                  102a cyclohexyl                                                                              H   H    H      4-tert.-butyl-                                                                              --                                                                phenylpropyl                                     103a cyclohexyl                                                                              H   H    H      3-tert.-butylbenzyl                                                                         --                                  104a 2-hydroxy-1,1-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         --                                       dimethyl-ethyl-                                                                cyclohexyl                                                                105a cyclohexyl                                                                              H   H    H      4-isopropylbenzyl                                                                           --                                  106a cyclohexyl                                                                              H   H    H      4-(2,4,4-trimethyl-                                                                         --                                                                pentyl)benzyl                                    107a 4-tert.-butyl-                                                                          H   H    H      4-tert.-amylbenyzl                                                                          --                                       cyclohexyl                                                                108a 1-methoxy-1-                                                                            H   H    H      4-tert.-butyoxybenzyl                                                                       --                                       methylethyl-                                                                   cyclhexyl                                                                 109a cyclohexyl                                                                              H   H    H      4-(1-methoxy-1-methyl-                                                                      --                                                                ethyl)benzyl                                     110a cyclohexyl                                                                              H   H    H      4(1-hydroxy-1-methyl-                                                                       --                                                                ethyl)benzyl                                     111a cyclohexyl                                                                              H   H    H      4-isopropenyl-benzyl                                                                        --                                  112a cyclohexyl                                                                              H   H    H      4-n-butoxy-benzyl                                                                           --                                  113a 4-tert.-amyl-                                                                           H   H    H      4-tert.-butylbenzyl                                                                         --                                       cyclohexyl                                                                114a cyclohexyl                                                                              H   H    H      2-methyl-4-tert.-                                                                           --                                                                butyl-benzyl                                     115a cyclohexyl                                                                              H   H    H      3,5,5-trimethylhexyl                                                                        --                                  116a cyclohexyl                                                                              H   H    H      6,10-14-trimethyl-                                                                          HI      3273, 3183, 2927,                                                              2855,                                                     pentadec-2-yl        1647, 1624, 1597,                                                              1533                        117a cyclohexyl                                                                              H   H    H      4-(4-tert.-butoxy-                                                                          HI      2974, 2930, 1608,                                                              1450,                                                     phenyl)-but-2-yl     1365, 1161                  118a cyclohexyl                                                                              H   H    H      2-(4-tert.-butyl-                                                                           HI      3291, 3220, 3173,                                                              2965,                                                     phenyl)-ethyl        2952, 2931, 1640,                                                              1633                        119a cyclohexyl                                                                              H   H    H      3-chlorobenzyl                                                                              HI      3249, 3178, 2931,                                                              2854,                                                                          1647, 1625, 1597,                                                              1576                        120a cyclohexyl                                                                              H   H    H      5-methyl-oct-2-yl                                                                           --                                  121a cyclohexyl                                                                              H   H    H      2,4,5-trimethoxybenzyl                                                                      --                                  122a cyclohexyl                                                                              H   H    H      4-methoxybenzyl                                                                             --                                  123a 4-(1-methoxy-                                                                           H   H    H      4-tert.-butylcyclohexyl                                                                     --                                       1-methyl)ethyl-                                                                cyclohexyl                                                                124a cyclohexyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    --      2958, 2928, 2854,                                                              1615,                                                     2-methylpropyl       1570, 1510, 1450,                                                              1363                        125a cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 =                                                                   3-(6-methylhept-2-yl)-                                                                      --      2952, 2926, 2853,                                                              1591,                                                     pyrrolidinyl         1542, 1518, 1449,                                                              1364                        126a cyclohexyl                                                                              H   H    H      benzyl       HI      134° C.              127a cyclohexyl                                                                              H   H    H      n-undecyl    HI      3283, 3251, 3182,                                                              2927,                                                                          2854, 1647, 1630,                                                              1452                        128a cyclohexyl                                                                              H   H    H      n-tetradecyl HI      3251, 3180, 2925,                                                              2854, 1648, 1631            129a cyclohexyl                                                                              H   H    H      oct-2-yl     HI      3275, 3182, 2929,                                                              2855,                                                                          1647, 1624, 1600,                                                              1553                        130a cyclohexyl                                                                              H   H    H      4-phenylbutyl                                                                               HI      3277, 3182, 3084,                                                              2932,                                                                          2856, 1648, 1630,                                                              1452                        131a cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 =                                                                   4-(2,6-dimethyl)-                                                                           HI      150° C.                                            morpholinyl                                      132a cyclohexyl                                                                              H   H    H      n-dodecanyl  HI      3248, 3180, 2924,                                                              2853, 1647, 1631            133a cyclohexyl                                                                              H   H    H      2,3-dimethoxy-benzyl                                                                        HI      178° C.              134a cyclohexyl                                                                              H   H    H      4-bromobenzyl                                                                               HI      3369, 3312, 3246,                                                              3188,                                                                          2931, 1651, 1624,                                                              1489                        135a cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 =                                                                   3-methyl-4-(4-tert.-bu-                                                                     HI      128° C.                                            tylphenyl)-pyrrolidinyl                          136a cyclohexyl                                                                              H   H    H      3,4-dichlorobenzyl                                                                          HI      3281, 3179, 2930,                                                              1648, 1624, 1470            137a cyclohexyl                                                                              H   H    H      2-chlorobenzyl                                                                              HI      3248, 3174, 2930,                                                              2854,                                                                          1646, 1625, 1444            138a cyclohexyl                                                                              H   H    R.sup.3 + R.sup.4 =                                                                   4-(4-tert-butylphenyl)-                                                                     HI      205° C.                                            piperidinyl                                      139a cyclohexyl                                                                              H   H    CH.sub.3                                                                              2,5,7,7-tetramethyl-                                                                        HI      3300, 3194, 3166,                                                              2950                                                      octyl                2932, 1638, 1616,                                                              1544                        140a cyclohexyl                                                                              H   H    H      4-(1,1,3,3-tetramethyl-                                                                     HI       75° C.                                            butyl)-benzyl                                    141a cyclohexyl                                                                              H   H    H      n-pentyl     HI      3281, 3250, 3182,                                                              2930,                                                                          2856, 1646, 1629,                                                              1600                        142a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         H.sub.3 BO.sub.3                                                                        72° C.              143a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         acetyl  3282, 3184, 2932,                                                              2855,                                                                  acetonate                                                                              1646, 1629, 1451            144a cyclohexyl                                                                              H   H    H      4-tert.-butylbeznyl                                                                         o-hydroxy-                                                                              52° C.                                                         phenol                              145a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         C.sub.6 H.sub.5COOH                                                                     70° C.              146a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         CCl.sub.3COOH                                                                          3317, 3197, 2935,                                                              2859.                                                                          1659, 1633, 1324, 832       147a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         3,4,5-  125° C.                                                         (OH).sub.3                                                                     C.sub.6 H.sub.5COOH                 148a cyclohexyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         H.sub.2 CO.sub.3                                                                        87° C.              149a cyclohexyl                                                                              H   H    H      4-(1,1,2-trimethyl-                                                                         HCl     180° c.                                            propyl)-benzyl                                   150a cyclohexyl                                                                              H   H    H      4-(1,1,2-trimethyl-                                                                         CH.sub.3 COOH                                                                          250° C.                                            propyl)-benzyl                                   151a cyclohexyl                                                                              H   H    H      4-(1,1,2-trimethyl-                                                                         C.sub.2 H.sub.2 O.sub.4                                                                 75° C.                                            propyl)-benzyl                                   152a cyclohexyl                                                                              H   H    H      n-tridecyl   HCl     120° C.              153a cyclohexyl                                                                              H   H    H      n-tridecyl   CH.sub.3 COOH                                                                          3173, 2925, 2853,                                                              1651,                                                                          1569, 1465, 1452,                                                              1404                        154a cyclohexyl                                                                              H   H    H      n-tridecyl   C.sub.2 H.sub.2 O.sub.4                                                                3299, 3191, 2925,                                                              2853,                                                                          1636, 1465, 1453,                                                              1218, 720                   155a cyclohexyl                                                                              H   H    H      6,10-dimethyl-undec-                                                                        HCl     120° C.                                            2-yl                                             156a cyclohexyl                                                                              H   H    H      6,10-dimethyl-undec-                                                                        CH.sub.3 COOH                                                                          3272, 3175, 2928,                                                              2856,                                                     2-yl                 1571, 1450, 1402,                                                              1014                        157a cyclohexyl                                                                              H   H    H      6,10-dimethyl-undec-                                                                        C.sub.2 H.sub.2 O.sub.4                                                                3272, 3189, 2929,                                                              1628,                                                     2-yl                 1603, 1403, 1191, 720       158a 4-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         --      2958, 2862, 1636,                cyclohexyl                                    1512, 1365                  159a 4-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   2-methyl-3-(4-tert.-                                                                        HI      245° C.                   cyclohexyl               butylphenyl)-pyrrolidinyl                        160a 4-tert.-butyl-                                                                          H   H    H      3-(morpholin-4-yl)-                                                                         HI      3276, 3186, 2947,                                                              2860,                            cyclohexyl               prop-1-yl            1630, 1450, 1141,                                                              1116                        161a 4-tert.-butyl-                                                                          H   H    CH.sub.3                                                                              2,5,7,7-tetramethyl-                                                                        HI      202° C.                   cyclohexyl               octyl                                            162a 4-tert.-butyl-                                                                          H   H    H      2,4-dicholorobenzyl                                                                         HI      163° C.                   cyclohexyl                                                                163a 4-tert.-butyl-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         HCl     162° C.                   cyclohexyl                                                                164a 4-tert.-butyl-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          170° C.                   cyclohexyl                                                                165a 4-tert.-butyl-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                                102° C.                   cyclohexyl                                                                166a 3-methyl-                                                                               H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         --      2955, 2925, 2867,                cyclohexyl                                    1636, 1512, 1458            167a 2-methyl-                                                                               H   H    H      4-tert.-butylbenzyl                                                                         HI      144° C.                   cyclohexyl                                                                168a 3-methyl-                                                                               H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HCl     142° C.                   cyclohexyl                                                                169a 3-methyl-                                                                               H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          102° C.                   cyclohexyl                                                                170a 3-methyl-                                                                               H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                                173° C.                   cyclohexyl                                                                171a 3-methyl-                                                                               H   H    H      6,10-dimethylundec-                                                                         CH.sub.3 COOH                                                                          3179, 3092, 2951,                                                              2927,                            cyclohexyl               2-yl                 2867, 1644, 1557,                                                              1460                        172a 2,6-dimethyl-                                                                           H   H    H      3-(4-tert.-butylphenyl)-                                                                    HI      3188, 2960, 2929,                cyclohexyl               2-methylpropyl       2871, 1569, 1463            173a 4-hyrdroxy                                                                              H   H    H      4-tert.-butylbenzyl                                                                         HI      100° C.                   cyclohexyl                                                                174a 3-methyl-                                                                               H   H    H      4-tert.-butylbenzyl                                                                         HCl     130° C.                   cyclohexyl                                                                175a 3-methyl-                                                                               H   H    H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          105° C.                   cyclohexyl                                                                176a 3-methyl-                                                                               H   H    H      4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                                 95° C.                   cyclohexyl                                                                177a 3,3-dimethyl-                                                                           H   H    H      3-(4-tert.-butylphenyl)-                                                                    HCl     100° C.                   cyclohexyl               2-methylpropyl                                   178a 3,3-dimethyl-                                                                           H   H    H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          100° C.                   cyclohexyl               2-methylpropyl                                   179a 3,3-dimethyl-                                                                           H   H    H      3-(4-tert.-butylphenyl)-                                                                    C.sub.2 H.sub.2 O.sub.4                                                                112° C.                   cyclohexyl               2-methylpropyl                                   180a cyclopentyl                                                                             H   H    H      4-tert.-butylbenzyl                                                                         HI       88° C.              181a cyclopentyl                                                                             H   H    H      3-(4-tert.-butylbenzyl)-                                                                    CH.sub.3 COOH                                                                          3304, 3184, 3089,                                                              2962,                                                     2-methylpropyl       2871, 1650, 1561,                                                              1401                        182a cyclopentyl                                                                             H   H    H      6,10-dimethylundec-2-yl                                                                     CH.sub.3 COOH                                                                          3175, 2955, 2927,                                                              2869,                                                                          1646, 1560, 1400            183a cycloheptyl                                                                             H   H    H      4-tert.-butylbenzyl                                                                         HI      3253, 3180, 2960,                                                              2927,                                                                          2857, 1645, 1626,                                                              1460                        184a cyclooctyl                                                                              H   H    H      4-tert.-butylbenzyl                                                                         HI       90° C.              185a cyclooctyl                                                                              H   H    H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          3186, 3091, 2961,                                                              2924,                                                     2-methylpropyl       2868, 1649, 1561,                                                              1404                        186a cyclooctyl                                                                              H   H    H      6,10-dimethyl-undec-                                                                        CH.sub.3 COOH                                                                          2951, 2925, 2867,                                                              1643,                                                     2-yl                 1559, 1465, 1400            187a cyclohexyl                                                                              H   isopropyl                                                                           H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                           72° C.              188a cyclohexyl                                                                              H   but-2-yl                                                                            H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                           80° C.              1b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-(4-tert.-butylphenyl)-                                                                    HCl     125° C.                   benzyl                   2-methylpropyl                                   2b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            R.sup.3 + R.sup.4 = 4-tert.-butyl-                                                                 HI      155° C.                   benzyl            piperidinyl                                             3b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         --      2963, 2904, 2867,                                                              1863,                            benzyl                                        1637, 1513, 1476,                                                              1464                        4b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HCl     125° C.                   benzyl                                                                    5b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         CH.sub. 3 COOH                                                                         2963, 2905, 1638,                                                              1568,                            benzyl                                        1514, 1477, 1393,                                                              1365                        6b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      cyclohexylmethyl                                                                            HI      186° C.                   benzyl                                                                    7b   p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3,5,5-trimethylhexyl                                                                        HI      165° C.                   benzyl                                                                    8b   benzyl   H   n-butyl                                                                             H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          2958, 2928, 2869,                                                              1639,                                                     2-methylpropyl       1510, 1495, 1453,                                                              1362                        9b   p-tert.-butyl-                                                                          H   n-butyl                                                                             R.sup.3 + R.sup.4 = cis-2,6-dimethyl-                                                              CH.sub.3 COOH                                                                          2963, 2935, 2872,                                                              1627,                            benzyl            morpholin-4-yl              1590, 1269, 1087            10b  p-tert.-butyl-                                                                          H   n-butyl                                                                             R.sup.3 + R.sup.4 = cis-2,6-dimethyl-                                                              HCl      60° C.                   benzyl            morpholin-4-yl                                          11b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      2,2-dimethylpropyl                                                                          HCl      88° C.                   benzyl                                                                    12b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      2,2-dimethylpropyl                                                                          CH.sub.3 COOH                                                                          2962, 2872, 1630,                                                              1574,                            benzyl                                        1394, 1366                  13b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                          2962, 2906, 1634,                                                              1570,                            benzyl                                        1394                        14b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         HCl     102° C.                   benzyl                                                                    15b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      3-(4-tert.-butylphenyl)-                                                                    HCl      95 to 100° C.            benzyl                   2-methylpropyl                                   16b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          2962, 2933, 1633,                                                              1571,                            benzyl                   2-methylpropyl       1394, 1364                  17b  p-tert.-butyl-                                                                          H   n-butyl                                                                             H      n-pentyl     --                                       benzyl                                                                    18b  p-tert.-butyl-                                                                          H   H    H      n-hexyl      HI      156° C.                   benzyl                                                                    19b  p-tert.-butyl-                                                                          H   H    H      n-heptyl     HI      135° C.                   benzyl                                                                    20b  p-tert.-butyl-                                                                          H   H    H      n-octyl      HI      113° C.                   benzyl                                                                    21b  p-tert.-butyl-                                                                          H   H    H      n-nonyl      HI      3247, 3179, 2956,                                                              2924,                            benzyl                                        2854, 1649, 1629,                                                              1465                        22b  p-tert.-butyl-                                                                          H   H    H      n-decyl      HI      3248, 3179, 2957,                                                              2925,                            benzyl                                        2855, 1649, 1630,                                                              1466                        23b  p-tert.-butyl-                                                                          H   H    H      n-dodecyl    HI      3247, 3180, 2957,                                                              2924,                            benzyl                                        2854, 1649, 1630,                                                              1466                        24b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-hexyl      HI      177° C.                   benzyl                                                                    25b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-octyl      HI      122° C.                   benzyl                                                                    26b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-decyl      HI       85° C.                   benzyl                                                                    27b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-dodecyl    HI       96° C.                   benzyl                                                                    28b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      2,2-dimethylpropyl                                                                          HI      165° C.                   benzyl                                                                    29b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-methyl-butyl                                                                              HI      137° C.                   benzyl                                                                    30b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            R.sup.3 + R.sup.4 = piperidinyl                                                                    HI       82° C.                   benzyl                                                                    31b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      phenethyl    HI       87° C.                   benzyl                                                                    32b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      benzyl       HI      124° C.                   benzyl                                                                    33b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-(4-tert.-butylphenyl)-                                                                    HI      165° C.                   benzyl                   2-methylpropyl                                   34b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      2-ethyl-hexyl                                                                               HI       65° C.                   benzyl                                                                    35b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-tridecyl   HI      105° C.                   benzyl                                                                    36b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-methoxy-phenethyl                                                                         HI      137° C.                   benzyl                                                                    37b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      6-ethyl-4-oxa-decyl                                                                         HI      3218, 2959, 2929,                                                              2870,                            benzyl                                        1623, 1462, 1380,                                                              1109                        38b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-phenyl-but-2-yl                                                                           HI      102° C.                   benzyl                                                                    39b  p-tert.-butoxy-                                                                         H   H    H      4-tert.-butyl-cyclo-                                                                        HI      192° C.                   benzyl                   hexylmethyl                                      40b  p-tert.-butyl-                                                                          H   H    H      4-tert.-butyl-cyclo-                                                                        HI      192° C.                   benzyl                   hexylmethyl                                      41b  p-tert.-butyl-                                                                          H   H    H      1-phenyl-ethyl                                                                              HI       70° C.                   benzyl                                                                    42b  p-tert.-butyl-                                                                          H   H    H      4-phenyl-but-2-yl                                                                           HI       75° C.                   benzyl                                                                    43b  p-tert.-butyl-                                                                          H   H    H      3-diethylaminopropyl                                                                        HI      3243, 3179, 2964,                                                              2870,                            benzyl                                        2822, 1629, 1465,                                                              1366                        44b  p-tert.-butyl-                                                                          H   H    H      4-methoxy-phenethyl                                                                         HI      3303, 3185, 3164,                                                              1643,                            benzyl                                        1632, 1595, 1512,                                                              1242                        45b  p-tert.-butyl-                                                                          H   H    H      phenethyl    HI      130° C.                   benzyl                                                                    46b  p-tert.-butyl-                                                                          H   H    H      2-ethylhexyl HI      3251, 3181, 2960,                                                              2929,                            benzyl                                        2872, 1649, 1630,                                                              1464                        47b  p-tert.-butyl-                                                                          H   H    H      benzyl       HI       58° C.                   benzyl                                                                    48b  p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 = 4-tert.-butyl-                                                                 HI      183° C.                   benzyl            piperidinyl                                             49b  p-tert.-butyl-                                                                          H   H    H      4-tert.-butylbenzyl                                                                         HI      182° C.                   benzyl                                                                    50b  p-tert.-butyl-                                                                          H   H    H      3-(4-tert.-butylphenyl)-                                                                    HI      152° C.                   benzyl                   2-methylpropyl                                   51b  p-tert.-butyl-                                                                          H   H    H      tridecyl     HI       89° C.                   benzyl                                                                    52b  p-tert.-butyl-                                                                          H   H    H      6-ethyl-4-oxa-decyl                                                                         HI      100° C.                   benzyl                                                                    53b  p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =piperidinyl                                                                     HI       72° C.                   benzyl                                                                    54b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butyl-cyclo-                                                                        HI      125° C.                   benzyl                   hexylmethyl                                      55b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-diethylaminpropyl                                                                         HI      3210, 3102, 2964,                                                              2870,                            benzyl                                        1620, 1458, 1383,                                                              1364                        56b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      1-phenyl-ethyl                                                                              HI      163° C.                   benzyl                                                                    57b  p-(1,1-dimethyl-                                                                        H   H    H      n-hexyl      --                                       ethyl)-benzyl                                                             58b  p-(1,1-dimethyl-                                                                        H   H    H      n-heptyl     --                                       ethyl)-benzyl                                                             59b  p-(1,1-dimethyl-                                                                        H   H    H      n-octyl      --                                       ethyl)-benzyl                                                             60b  p-(1,1-dimethyl-                                                                        H   H    H      n-nonyl      --                                       ethyl)-benzyl                                                             61b  p-(1,1-dimethyl-                                                                        H   H    H      tert.-butylbenzyl                                                                           --                                       ethyl)-benzyl                                                             62b  p-(1,1-dimethyl-                                                                        H   H    H      3-methylbutyl                                                                               --                                       ethyl)-benzyl                                                             63b  p-(1,1-dimethyl-                                                                        H   H    H      3-(4-tert.-butylphenyl)-                                                                    --                                       ethyl)-benzyl            2-methylpropyl                                   64b  p-tert.-butoxy-                                                                         H   H    H      n-hexyl      --                                       benzyl                                                                    65b  p-tert.-butoxy-                                                                         H   H    H      n-heptyl     --                                       benzyl                                                                    66b  p-tert.-butoxy-                                                                         H   H    H      n-octyl      --                                       benzyl                                                                    67b  p-tert.-butoxy-                                                                         H   H    H      n-nonyl      --                                       benzyl                                                                    68b  p-tert.-butoxy-                                                                         H   H    H      n-decyl      --                                       benzyl                                                                    69b  p-tert.-butoxy-                                                                         H   H    H      3-methylbutyl                                                                               --                                       benzyl                                                                    70b  p-tert.-butoxy-                                                                         H   H    H      tert.-butylbenzyl                                                                           --                                       benzyl                                                                    71b  p-tert.-butoxy-                                                                         H   H    H      tert.-buoxybenzyl                                                                           --                                       benzyl                                                                    72b  p-tert.-butoxy-                                                                         H   H    H      n-octyl      --                                       benzyl                                                                    73b  p-(1,1,2-tri-                                                                           H   H    H      n-hexyl      --                                       methylpropyl)-                                                                 benzyl                                                                    74b  p-(1,1,2-tri-                                                                           H   H    H      n-heptyl     --                                       methylpropyl)-                                                                 benzyl                                                                    75b  p-(1,1,2-tri-                                                                           H   H    H      n-octyl      --                                       methylpropyl)-                                                                 benzyl                                                                    76b  p-(1,1,2-tri-                                                                           H   H    H      n-nonyl      --                                       methylpropyl)-                                                                 benzyl                                                                    77b  p-(1,1,2-tri-                                                                           H   H    H      n-decyl      --                                       methylpropyl)-                                                                 benzyl                                                                    78b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      cyclohexylmethyl                                                                            HCl     155° C.                   benzyl                                                                    79b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      cyclohexylmethyl                                                                            CH.sub.3 COOH                                                                           82° C.                   benzyl                                                                    80b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      cyclohexylmethyl                                                                            (COOH).sub.2                                                                           1/3° C.                   benzyl                                                                    81b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3,5,5-trimethylhexyl                                                                        (COOH).sub.2                                                                           180° C.                   benzyl                                                                    82b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3,5,5-trimethylhexyl                                                                        CH.sub.3 COOH                                                                           75° C.                   benzyl                                                                    83b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3,5,5-trimethylhexyl                                                                        HCl     107° C.                   benzyl                                                                    84b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-hexyl      HCl     105° C.                   benzyl                                                                    85b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-hexyl      CH.sub.3 COOH                                                                          110° C.                   benzyl                                                                    86b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-hexyl      (COOH).sub.2                                                                           185° C.                   benzyl                                                                    87b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-methylbutyl                                                                               (COOH).sub.2                                                                           182° C.                   benzyl                                                                    88b  p-tert.-butyl-                                                                          H   H    H      3-methylbutyl                                                                               CH.sub.3 COOH                                                                           72° C.                   benzyl                                                                    89b  p-tert.-butyl-                                                                          H   H    H      3-methylbutyl                                                                               HCl     105° C.                   benzyl                                                                    90b  p-tert.-butyl-                                                                          H   H    H      6-ethyl-4-oxa-decyl                                                                         HCl     oil, 3260, 3173, 2959,                                                         2930,                            benzyl                                        2871, 1655, 1637,                                                              1464                        91b  p-tert.-butyl-                                                                          H   H    H      6-ethyl-4-oxa-decyl                                                                         CH.sub.3 COOH                                                                          oil, 2959, 2929, 2870,                                                         1653,                            benzyl                                        1560, 1515, 1403,                                                              1110                        92b  p-tert.-butyl-                                                                          H   H    H      6-ethyl-4-oxa-decyl                                                                         (COOH).sub.2                                                                           oil, 3183, 2958, 2929,                                                         2870,                            benzyl                                        1633, 1462, 1220,                                                              1109                        93b  p-tert.-butyl-                                                                          H   H    H      4-tert.-butoxybenzyl                                                                        (COOH).sub. 2                                                                          118° C.                   benzyl                                                                    94b  p-tert.-butyl-                                                                          H   H    H      4-tert.-butoxybenzyl                                                                        CH.sub.3 COOH                                                                          168° C.                   benzyl                                                                    95b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-(tert.-butylphenyl)-                                                                      CH.sub.3 COOH                                                                           97° C.                   benzyl                   2-methylpropyl                                   96b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-(4-tert.-butylphenyl)-                                                                    H.sub.3 BO.sub.3                                                                       149° C.                   benzyl                   2-methylpropyl                                   97b  p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      3-(4-tert.-butylphenyl)-                                                                    --      2960, 2903, 2867,                                                              1636,                            benzyl                   2-methylpropyl       1512, 1474, 1462,                                                              1362                        98b  p-tert.-butyl-                                                                          H   H    H      2-ethylhexyl HCl      80° C.                   benzyl                                                                    99b  p-tert.-butyl-                                                                          H   H    H      2-ethylhexyl CH.sub.3 COOH                                                                          2959, 2928, 2870,                                                              1569,                            benzyl                                        1462, 1402, 1363,                                                              1269                        100b p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   4-tert.-butyl-                                                                              HCl     250° C.                   benzyl                   piperidinyl                                      101b p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   4-tert.-butyl-                                                                              CH.sub.3 COOH                            benzyl                   piperidinyl                                      102b p-tert.-butyl-                                                                          H   H    H      3-(4-tert.-butylphenyl)-                                                                    HCl      90° C.                   benzyl                   2-methylpropyl                                   103b p-tert.-butyl-                                                                          H   H    H      3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                          3278, 3198, 2961,                                                              1635,                            benzyl                   2-methylpropyl       1606, 1561, 1516,                                                              1409                        104b p-tert.-butyl-                                                                          H   H    H      4-hydroxybenzyl                                                                             HCl     3323, 3263, 3170,                                                              2961,                            benzyl                                        1651, 1614, 1513,                                                              1267                        105b p-tert.-butyl-                                                                          H   H    H      4-hydroxybenzyl                                                                             CH.sub.3 COOH                                                                          3180, 3026, 2962,                                                              1645,                            benzyl                                        1614, 1554, 1462,                                                              1409                        106b p-tert.-butyl-                                                                          H   H    CH.sub.3                                                                              2,5,7,7-tetramethyl-                                                                        HI       58° C.                   benzyl                   octyl                                            107b p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      4-tert.-butylbenzyl                                                                         HI       90° C.                   benzyl                                                                    108b p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   3-(1,5-dimethylhexyl)-                                                                      HJ      172° C.                   benzyl                   pyrrolidinyl                                     109b p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   3-(1,5-dimethylhexyl)-                                                                      HCl     190° C.                   benzyl                   pyrrolidinyl                                     110b p-tert.-butyl-                                                                          H   H    R.sup.3 + R.sup.4 =                                                                   3-(1,5-dimethylhexyl)-                                                                      CH.sub.3 COOH                                                                          2955, 2928, 2868,                                                              1610,                            benzyl                   pyrrolidinyl         1573, 1465, 1448,                                                              1402                        111b p-tert.-butyl-                                                                          H   H    H      n-undecyl    HI      3249, 3181, 2956,                                                              2924,                            benzyl                                        2853, 1649, 1629,                                                              1464                        112b p-tert.-butyl-                                                                          H   H    H      6-hydroxyhexyl                                                                              HI      3287, 3198, 2932,                                                              2859,                            benzyl                                        1650, 1629, 1547,                                                              1462                        113b p-tert.-butyl-                                                                          H   H    H      2-(2-hydroxyethoxy)-                                                                        HI      3299, 3188, 2958,                                                              2869,                            benzyl                   ethyl                1651, 1631, 1122,                                                              1065                        114b p-tert.-butyl-                                                                          H   H    H      6-hydroxy-6-methyl-hept-                                                                    HI      3297, 3188, 2964,                                                              2867,                            benzyl                   2-yl                 1626, 1602, 1556,                                                              1462                        115b p-tert.-butyl-                                                                          H   H    H      6,10-dimethyl-undec-                                                                        HI      3249, 3180, 2954,                                                              2926,                            benzyl                   2-yl                 2867, 1646, 1626,                                                              1462                        116b p-tert.-butyl-                                                                          H   H    H      2,2-dimethylpropyl                                                                          HI       85° C.                   benzyl                                                                    117b p-tert.-butyl-                                                                          H   H    H      3-methylbutyl                                                                               HI      122° C.                   benzyl                                                                    118b p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-butyl      HI      135° C.                   benzyl                                                                    119b p-tert.-butyl-                                                                          H   CH.sub.3                                                                            H      n-pentyl     HI      147° C.                   benzyl                                                                    120b p-tert.-butyl-                                                                          H   n-butyl                                                                             H      cis-2,6-dimethyl-morpholin-                                                                 --      2962, 2931, 2904,                                                              2869,                            benzyl                   4-yl                 1637, 1375, 1144,                                                              1086                        121b p-tert.-butyl-                                                                          H   n-butyl                                                                             H      2,2-dimethylpropyl                                                                          --      2956, 2904, 2867,                                                              1649,                            benzyl                                        1513, 1476, 1464,                                                              1362                        122b p-tert.-butyl-                                                                          H   n-butyl                                                                             H      4-tert.-butylbenzyl                                                                         --      2959, 2931, 2904,                                                              2868,                            benzyl                                        1633, 1513, 1463,                                                              1362                        123b p-tert.-butyl-                                                                          H   n-butyl                                                                             H      3-(4-tert.-butylphenyl)-                                                                    --      2960, 2928, 2869,                                                              1640,                            benzyl                   2-methylpropyl       1512, 1462, 1362,                                                              1269                        124b p-tert.-butyl-                                                                          H   H    H      n-butyl      HI      3248, 3182, 2959,                                                              2932,                            benzyl                                        2870, 1649, 1630,                                                              1463                        125b p-tert.-butyl-                                                                          H   H    H      n-pentyl     HI      120° C.                   benzyl                                                                    __________________________________________________________________________

Use examples

The active ingredients N-1-(4-tert-butylphenyl)-N-3-allylguanidine (A), N-1-(4-tert-butylphenyl)-N-2-cyclohexyl-n-3-N,N-dimethylamino-n-propyl)guanidine (B) and N-1-(4-tert-butylphenyl)-N-2-DE-A 31 08 564 were used for comparison purposes.

Example 1 Action on Pyrenophora teres

Barley seedlings of the "Igri" variety were sprayed to runoff at the two-leaf stage with aqueous suspensions consisting (dry basis) of 80% of active ingredient and 20% of emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophara teres, and set up for 48 hours in a high-humidity climatic cabinet at 18° C. The plants were then cultivated for a further 5 days in the greenhouse at 20 to 22° and a relative humidity of 70° C. The extend of fungus spread was then assessed.

The results show that active ingredients, 1a, 5a, 7a, 11a, 13a, 27a, 28a, 31a, 32a, 39a, 49a, 54a, 57a, 75a, 1b, 3b, 4b, 7b, 8b, 13b, 14b, 15b, 16b, 18b, 20b, 22b, 23b, 25b, 26b, 34b, 37b, 52b, and 54b, applied as 0.05wt% spray liquors, have a better fungicidal action (85%) than prior art comparative ingredients A, B and C (55%).

Example 2 Action on wheat mildew

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were sprayed with 0.025% aqueous spray liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier, and dusted, 24 hours after the sprayed-on liquor had dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants were then set up in the greenhouse at from 20 to 22° C. and a relative humidity of 75 to 80%. The extent of fungus spread was assessed after 7 days.

The results show that active ingredients 1a, 15a, 26a, 32a, 47a, 49a, 56a, 69a, 70a, 2b, 6b, 9b, 11b, 12b, 13b, 29b, 31b, 34b, 35b, 36b, 38b, 45b and 46b, applied as 0.025wt% spray liquors, have a better fungicidal action (85%) than prior art comparative ingredients B and C (60%0. 

We claim:
 1. A substituted guanidine of formula I ##STR20## where: is cycloalky which has 5 to 12 carbon atoms in the ring and may carry up to three of the following substituents: hydroxyl, halogen, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -haloalkyl and C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl;R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl, and R⁴ is C₅ -C₁₈ -alkyl which may be interrupted by oxygen, or is a C₅ -C₁₈ -alkenyl group, a C₄ -C₁₈ -alkynyl group or phenyl-C₁ -C₆ -alkyl group, where these groups may carry up to three of the following substituents: hydroxyl, halogen, cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino substituents, and the phenyl moiety of the phenylalkyl group may additionally carry a phenoxy group or up to three C₂ -C₄ -alkenyl groups, C₁ -C₄ -alkoxy-C₁ -C₄ alkyl groups or C₁ -C₆ -alkyl groups which may be unsubstituted or partially or completely halogenated, or C₅ -C₆ -cycloalkyl-C₁ -C₈ -alkyl where the cycloalkyl ring may carry up to three C₁ -C₄ -alkyl groups or up to two hydroxyl or trifluoromethyl groups; or the plant tolerated mineral acid slats or metal complexes thereof.
 2. A guanidine as set forth in claim 1, where the substituents have the following meanings:is cycloalkyl which has 5 to 12 carbon atoms in the ring and may carry up to three of the following substituents: hydroxyl, fluoro, chloro, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl and C₁ -C₆ -alkoxy-C₁ -C₅ -alkyl; R¹, R² and R³ are each hydrogen or C₁ -C₄ alkyl; R⁴ is C₅ -C₁₈ -alkyl which may be interrupted by oxygen, or is C₅ -C₁₈ -alkenyl, C₄ -C₁₈ -alkynyl or phenyl-C₁ -C₆ -alkyl, where these groups may carry up to three of the following substituents: hydroxyl, chloro, bromo, cyano or C₁ -C₇ -alkoxy, or up to two amino, C₁ -C₄ -alkylamino or di-(C₁ -C₄ -)-alkyl-amino substituents, and the phenyl moiety of the phenylalkyl group may additionally carry a phenoxy group or up to three C₂ -C₄ -alkenyl groups, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl groups or C₁ -C₄ -alkyl groups which may be unsubstituted or partially or completely halogenated; or C₅ -C₆ -cycloalkyl-C₁ -C₄ -alkyl groups or up to two trifluoromethy groups;or the plant-tolerted mineral acid salts or metal complexes thereof.
 3. A fungicidal composition comprising a fungicidally effective amount of at least one substituted guanidine of the formula I, as set forth in claim 1, or a plant-tolerated mineral acid salt or metal complex thereof and a liquid or solid carrier.
 4. A process for combating fungi, wherein a fungicidally effective amount of a substituted guanidine of the Formula I, as set forth in claim 1, or a plant-tolerated mineral acid salt or metal complex thereof, is applied to fungi, or to plants or their habitat threatened by fungus attack, or on the seeds of the threatened plants.
 5. A substituted guanidine as set forth in claim 1, wherein A is cyclohexyl; R¹, R² and R³ are each hydrogen; and R⁴ is 4-tertiarybutylbenzyl.
 6. A substituted guanidine of formula I: R1 ? ? ##STR21## where: is cycloalkyl which has 5 to 12 carbon atoms in the ring and may carry up to three of the following substituents: halogen, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, and C₁ -C₁₀ -haloalkyl;R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl; and R⁴ is 4-tertiarybutylphenyl, C₁ -C₄ -alkyl or is C₅ -C₁₈ -alkyl which may carry up to three of the following substituents: halogen or C₁ -C₇ -alkoxy or up to two amino groups or the plant-tolerated salts or metal complexes thereof. 